Polymer production method

ABSTRACT

A polymer production method whereby: a flow reactor comprising a flow path wherein a plurality of liquids can be mixed is used; and a monomer is anionically polymerized in the presence of an initiator. The flow reactor comprises a mixer for mixing two liquids, said mixer comprising either a joint member having a double pipe therein or a static mixer member.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Divisional application of co-pending applicationSer. No. 16/075,283, filed on Aug. 3, 2018, which is the National Phaseunder 35 U.S.C. § 371 of International Application No.PCT/JP2017/003912, filed on Feb. 3, 2017, which claims the benefit under35 U.S.C. § 119(a) to Patent Application No. 2016-019733, filed in Japanon Feb. 4, 2016, all of which are hereby expressly incorporated byreference into the present application.

TECHNICAL FIELD

The present invention relates to a polymer production method.

BACKGROUND ART

Flow chemistry, which continuously carries out chemical synthesis in astream of flowing solution using a reaction apparatus referred to as aflow reactor or a microreactor, has been attracting attention in recentyears. Compared with conventionally used batch processes, flow chemistrycarries out reactions using a small reactor, and so advantages includethe ability for precise temperature control and a good mixingefficiency.

In flow synthesis involving the mixture of two liquids, undissolvedmatter often settles out in the mixing section (mixer), blocking theflow channel and giving rise to pressure fluctuations, which makeslong-term continuous operation impossible or causes the quality of theresulting synthesized product to be unstable. This problem is especiallypronounced in reaction systems that use organolithium reagents, as inthe anionic polymerization of polymers. Achieving both stable long-termcontinuous operation and highly efficient mixture is not easy.

PRIOR ART DOCUMENTS Patent Documents

Patent Document 1: JP-A 2009-067999

SUMMARY OF INVENTION Technical Problem

It is therefore an object of this invention to provide a method that iscapable of stably producing polymer for a long period of time.

Solution to Problem

In the course of extensive investigations aimed at achieving the aboveobject, the inventors have discovered that, by using a given flowreactor, polymer can be stably produced for a long period of time.

Accordingly, the invention provides the following polymer productionmethod.

-   1. A polymer production method which includes the step of    anionically polymerizing a monomer in the presence of an initiator    by using a flow reactor having a flow channel capable of mixing a    plurality of liquids, wherein the flow reactor is equipped with a    mixer for mixing two liquids that includes a joint member having a    double tube at the interior or a static mixer member.-   2. The polymer production method of 1 above, wherein the static    mixer member has a tubular body and an element body inserted at the    interior of the tubular body.-   3. The polymer production method of 1 or 2 above, wherein the mixer    for mixing two liquids includes a joint member having a double tube    at the interior and a static mixer member.-   4. The polymer production method of 3 above,

wherein the mixer for mixing two liquids includes a joint member havinga double tube at the interior and a static mixer member;

the static mixer member has a tubular body and an element body insertedat the interior of the tubular body; and

the joint member and the static mixer member are connected in suchmanner that a double tube side endface of the tubular body is intouching contact with a static mixer member side endface of the doubletube.

-   5. The polymer production method of 4 above, wherein the static    mixer member side end of the double tube is situated at the interior    of the joint member.-   6. The polymer production method of any of 1 to 5 above, wherein the    joint member has an insertion hole for inserting an inner tube    through which flows an initiator solution and, in the inner    tube-inserted state, the double tube is formed of, at least near a    tip of the inner tube, the inner side of the inner tube and the    space defined by an outer wall of the inner tube and an inner wall    of the insertion hole.-   7. The polymer production method of 6 above, wherein the joint    member has a feed port for introducing a monomer solution, which    feed port is connected to the insertion hole.-   8. The polymer production method of 7 above, wherein the insertion    hole is formed so as to have, in the vicinity of a connecting    portion with the feed port, a diameter that is substantially the    same as the inner tube outside diameter, and moreover is formed so    as to have, from the place of connection to a tip of the inner tube,    a diameter that is larger than the inner tube outside diameter.-   9. The polymer production method of any of 6 to 8 above, wherein the    joint member has a hole for connecting to the static mixer member    and the feed port is connected to said connecting hole.-   10. The polymer production method of any of 2 to 9 above, wherein    the element body is inserted into the interior of the tubular body    in such manner that one end thereof is substantially flush with the    double tube side endface of the tubular body.-   11. The polymer production method of any of 2 to 10 above, wherein    the element body has a shape in which a plurality of right-handed    twist blades and left-handed twist blades mutually overlap in a    twist axis direction.-   12. The polymer production method of any of claims 1 to 11 above,    wherein the monomer is an aromatic vinyl compound.-   13. The polymer production method of any of 1 to 12 above, wherein    the initiator is an alkyllithium.-   14. The polymer production method of any of 1 to 13 above, wherein    the polymer has a dispersity of 1.5 or less.-   15. A polymer containing structural units of formula (1) below

(wherein R¹ is a hydrogen atom or a methyl group; R² to R⁶ are eachindependently a hydrogen atom, an alkoxy group of 1 to 5 carbon atoms,an alkyl group of 1 to 10 carbon atoms that may be substituted with ahalogen atom, —OSiR⁷ ₃ or —SiR⁷ ₃; and each R⁷ is independently an alkylgroup of 1 to 10 carbon atoms, a phenyl group, an alkoxy group of 1 to 5carbon atoms or an alkylsilyl group of 1 to 5 carbon atoms), wherein thepolymer has an end that is an n-butyl group from an initiator residue, aweight-average molecular weight of from 1,000 to 50,000, and adispersity is 1.5 or less.

-   16. The polymer of 14 above, wherein R⁴ is an alkoxy group of 1 to 5    carbon atoms or —SiR⁷ ₃.-   17. The polymer of 15 above, wherein R⁴ is a methoxy group or    —Si(CH₃)₃.-   18. A block copolymer comprising a first polymer block containing    structural units of formula (2) below and a second polymer block    containing structural units of formula (3) below

(wherein R¹¹ and R²¹ are each independently a hydrogen atom or a methylgroup; R¹² to R¹⁶ are each independently a hydrogen atom, an alkoxygroup of 1 to 5 carbon atoms or an alkyl group of 1 to 10 carbon atomswhich may be substituted with a halogen atom; R²² to R²⁶ are eachindependently a hydrogen atom, —OSiR²⁷ ₃ or —SiR²⁷ ₃; each R²⁷ isindependently an alkyl group of 1 to 10 carbon atoms, a phenyl group, analkoxy group of 1 to 5 carbon atoms or an alkylsilyl group of 1 to 5carbon atoms; and m and n are each independently an integer from 1 to480), wherein the structural units of formula (2) and the structuralunits of formula (3) are mutually differing structural units and thepolymer has an end that is an n-butyl group from an initiator residue, aweight-average molecular weight (Mw) of from 1,000 to 50,000, and adispersity of 1.5 or less.

-   19. The block copolymer of 18 above, wherein R¹⁴ is an alkoxy group    of 1 to 5 carbon atoms and R²⁴ is —SiR²⁷ ₃.-   20. The block copolymer of 19 above, wherein R¹⁴ is a methoxy group    and R²⁴ is —Si(CH₃)₃.

Advantageous Effects of Invention

Because the mixer for mixing two liquids used in this flow reactor doesnot readily clog and moreover has a good mixing efficiency, it ispossible to stably produce polymer over a long period of time by thepolymer production method of the invention using this mixer. Inparticular, block copolymers obtained by the production method of theinvention have a small dispersity Mw/Mn (meaning the molecular weightdistribution is narrow) and the structure can be controlled to a highdegree, making such polymers applicable to semiconductor lithographybased on induced self-assembly as well as to nanopatterning technology,or applicable to the production of high-performance elastomers.

BRIEF DESCRIPTION OF THE DIAGRAMS

FIG. 1 is a perspective view showing an embodiment of the mixer formixing two liquids that is used in the present invention.

FIG. 2 is an exploded perspective view of the mixer in FIG. 1.

FIG. 3 is a sectional view of the main body taken along line in FIG. 2.

FIG. 4 is a sectional view along line IV-IV in FIG. 1

FIG. 5 is an enlarged sectional view of the double tube portion in FIG.4.

FIG. 6 is a bottom view of the main body in the inner tube-insertedstate.

FIG. 7 is a view of the element body of the static mixer member, as seenfrom a direction perpendicular to the twist axis direction.

FIG. 8 is a perspective view showing an embodiment of the mixer formixing two liquids that is used in the invention.

FIG. 9 is a schematic diagram showing an embodiment of the flow reactorused in the invention.

FIG. 10 is a schematic diagram showing the construction of the flowreactor used in the Working Examples.

FIG. 11 is a graph showing the pressure trend during the reaction inWorking Example 1.

FIG. 12 is a graph showing the pressure trend during the reaction inWorking Example 2.

FIG. 13 is a graph showing the pressure trend during the reaction inWorking Example 3.

FIG. 14 is a graph showing the pressure trend during the reaction inWorking Example 4.

FIG. 15 is a graph showing the pressure trend during the reaction inWorking Example 5.

FIG. 16 is a ¹H-NMR chart of the polymer produced in Working Example 5.

FIG. 17 is a graph showing the pressure trend during the reaction inWorking Example 6.

FIG. 18 is a graph showing the pressure trend during the reaction inComparative Example 1.

FIG. 19 is a graph showing the pressure trend during the reaction inComparative Example 2.

DESCRIPTION OF EMBODIMENTS

The polymer production method of the invention uses a flow reactorhaving a flow channel which is capable of mixing together a plurality ofliquids to anionically polymerize monomer in the presence of aninitiator. The flow reactor is equipped with a mixer for mixing twoliquids that has a double tube at the interior.

[Monomer]

The monomer used in the polymer production method of the invention isnot particularly limited, so long as it is capable of anionicpolymerization. Such monomers are exemplified by aromatic vinylcompounds, conjugated dienes and (meth)acrylic compounds.

Exemplary aromatic vinyl compounds include styrene derivatives of thefollowing formula.

In the formula, R¹ is a hydrogen atom or a methyl group. R² to R⁶ areeach independently a hydrogen atom, an alkoxy group of 1 to 5 carbonatoms, an alkyl group of 1 to 10 carbon atoms which may be substitutedwith a halogen atom, —OSiR⁷ ₃ or —SiR⁷ ₃. Each R⁷ is independently analkyl group of 1 to 10 carbon atoms, a phenyl group, an alkoxy group of1 to 5 carbon atoms or an alkylsilyl group of 1 to 5 carbon atoms.

The alkyl group may be linear, branched or cyclic. Specific examplesinclude methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl,isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methylcyclopropyl,2-methylcyclopropyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl,n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl,1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl,1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl,1-ethyl-n-propyl, cyclopentyl, 1-methylcyclobutyl, 2-methylcyclobutyl,3-methylcyclobutyl, 1,2-dimethylcyclopropyl, 2,3-dimethylcyclopropyl,1-ethylcyclopropyl, 2-ethylcyclopropyl, n-hexyl, 1-methyl-n-pentyl,2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl,1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl,2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl,1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl,1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl,1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methylcyclopentyl,2-methylcyclopentyl, 3-methylcyclopentyl, 1-ethylcyclobutyl,2-ethylcyclobutyl, 3-ethylcyclobutyl, 1,2-dimethylcyclobutyl,1,3-dimethylcyclobutyl, 2,2-dimethylcyclobutyl, 2,3-dimethylcyclobutyl,2,4-dimethylcyclobutyl, 3,3-dimethylcyclobutyl, 1-n-propylcyclopropyl,2-n-propylcyclopropyl, 1-isopropylcyclopropyl, 2-i sopropylcyclopropyl,1,2,2-trimethylcyclopropyl, 1,2,3-trimethylcyclopropyl,2,2,3-trimethylcyclopropyl, 1-ethyl-2-methylcyclopropyl,2-ethyl-1-methylcyclopropyl, 2-ethyl-2-methylcyclopropyl and2-ethyl-3-methylcyclopropyl groups. Of these alkyl groups, ones havingfrom 1 to 8 carbon atoms are preferred, ones having from 1 to 6 carbonatoms are more preferred, and ones having from 1 to 3 carbon atoms areeven more preferred.

Specific examples of alkoxy groups include methoxy, ethoxy, n-propoxy,isopropoxy, cyclopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy,cyclobutoxy, 1-methylcyclopropoxy, 2-methylcyclopropoxy, n-pentyloxy,1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy,1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy,1-ethyl-n-propoxy, 1,1-diethyl-n-propoxy, cyclopentoxy,1-methylcyclobutoxy, 2-methylcyclobutoxy, 3-methylcyclobutoxy,1,2-dimethylcyclopropoxy, 2,3-dimethylcyclopropoxy, 1-ethylcyclopropoxyand 2-ethylcyclopropoxy groups. The alkoxy group structure is preferablylinear or branched. Of these, ones having from 1 to 3 carbon atoms arepreferred.

Preferred halogen atoms are fluorine, chlorine, bromine and iodineatoms, with fluorine and chlorine atoms being more preferred.

R⁴ is preferably an alkoxy group of 1 to 5 carbon atoms or —SiR⁷ ₃, andmore preferably a methoxy group or —Si(CH₃)₃. R², R³, R⁵ and R⁶ arepreferably hydrogen atoms, alkyl groups of 1 to 10 carbon atoms, alkoxygroups of 1 to 5 carbon atoms or −SiR⁷ ₃, and are more preferablyhydrogen atoms, methoxy groups or —Si(CH₃)₃.

Specific examples of the styrene derivatives include styrene,α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene,4-ethylstyrene, 2-ethylstyrene, 3-ethyl styrene, 4-tert-butyl styrene,4-dimethylsilylstyrene, 4-trimethylsilylstyrene,4-trimethylsilyloxystyrene, 4-dimethyl(tert-butyl)silylstyrene,4-dimethyl(tert-butyl)silyloxystyrene, 2-methoxystyrene,3-methoxystyrene, 4-methoxystyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, 2,6-dimethylstyrene, 2,4-dimethoxystyrene, 3,4-dimethoxystyreneand 3,4,5-trimethoxystyrene.

Preferred use can be made of vinylnaphthalene, vinylanthracene,2-vinylpyridine, 3-vinylpyridine and 4-vinylpyridine as the aromaticvinyl compound.

Examples of conjugated dienes include 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-heptadiene,1,3-hexadiene and 1,3-cyclohexadiene.

Examples of the (meth)acrylic compounds include methyl (meth)acrylate,ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,n-butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl(meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate,isopentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl(meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,n-decyl (meth)acrylate, isodecyl (meth)acrylate, n-dodecyl(meth)acrylate, n-stearyl (meth)acrylate, isostearyl (meth)acrylate,phenyl (meth)acrylate, benzyl (meth)acrylate, naphthyl (meth)acrylate,anthryl (meth)acrylate, anthrylmethyl (meth)acrylate, 2-phenylethyl(meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate,2,2,2-trichloroethyl (meth)acrylate, methoxydiethylene glycol(meth)acrylate, methoxypolyethylene glycol (meth)acrylate,tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate,n-butoxyethyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate,2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate,2-propyl-2-adamantyl (meth)acrylate, 2-methoxybutyl-2-adamantyl(meth)acrylate, 8-methyl-8-tricyclodecyl (meth)acrylate,8-ethyl-8-tricyclodecyl (meth)acrylate,5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone and2,2,3,3,4,4,4-heptafluorobutyl (meth)acrylate.

Of these, in terms of the ease of obtaining a monodisperse polymer evenat a relatively high temperature, preferred monomers include aromaticvinyl compounds and tert-butyl (meth)acrylate.

[Initiator]

The initiator used in the polymer production method of the invention isnot particularly limited, so long as it can normally be used in anionicpolymerization. Exemplary initiators include organolithium compounds,

Examples of organolithium compounds include monoorganolithium compoundssuch as methyllithium, ethyllithium n-propyllithium, isopropyllithium,n-butyllithium, isobutyllithium, sec-butyllithium, tert-butyllithium,pentyllithium, hexyllithium, methoxymethyllithium, ethoxymethyllithium,phenyllithium, naphthyllithium, benzyllithium, phenylethyllithium,α-methylstyryllithium, 1,1-diphenylhexyllithium,1,1-diphenyl-3-methylpentyllithium, 3-methyl-1,1-diphenylpentyllithium,vinyllithium, allyllithium, propenyllithium, butenyllithium,ethynyllithium, butynyllithium, pentynyllithium, hexynyllithium,2-thienyllithium, 4-pyridyllithium and 2-quinolyllithium; andpolyorganolithium compounds such as 1,4-dilithiobutane,1,5-dilithiopentane, 1,6-dilithiohexane, 1,10-dilithiodecane,1,1-dilithiodiphenylene, dilithiopolybutadiene, dilithiopolyisoprene,1,4-dilithiobenzene, 1,2-dilithio-1,2-diphenylethane,1,4-dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene and1,3,5-trilithio-2,4,6-triethylbenzene. Of these, monoorganolithiumcompounds such as n-butyllithium, sec-butyllithium and tert-butyllithiumare preferred.

[Flow Reactor]

The flow reactor is not particularly limited, so long as it is equippedwith a mixer for mixing two liquids that has a double tube at theinterior. However, a flow reactor of the following construction ispreferred. That is, the mixer for mixing two liquids preferably includesa joint member having a double tube at the interior or a static mixermember. The mixer more preferably includes both a joint member having adouble tube at the interior and a static mixer member. It is even morepreferable for the static mixer member to have a tubular body and anelement body inserted at the interior of the tubular body, and for thejoint member and the static mixer member to be connected in such mannerthat a double tube side endface of the tubular member is in touchingcontact with a static mixer member side endface of the double tube.

By having the joint member and the static mixer member connected in suchmanner that the double tube side endface of the tubular body is intouching contact with the static mixer member side endface of the doubletube, clogging does not readily arise and stable long-term continuousoperation of the mixer for mixing two liquids is possible, even whilemaintaining a good mixing efficiency.

That is, given that the mixer has a construction in which the doubletube and the tubular body of the static mixer are connected at the jointinterior, touching contact between the respective endfaces can be morereliably carried out than in a conventional microreactor construction.As a result, because the two liquids that have flowed out of the doubletube flow into the static mixer at substantially the same time as theyflow out of the double tube, more reliable mixture of the two liquids iscarried out at the time of reaction onset.

In the mixer for mixing two liquids, it is preferable for the staticmixer member side end of the double tube to be situated at the interiorof the joint member. This arrangement simplifies the double tubeconstruction, as a result of which the joint member is easy tomanufacture and the point of contact between the joint member and thestatic mixer member is easier to check.

In this mixer for mixing two liquids, it is preferable for the jointmember to have an insertion hole for inserting an inner tube throughwhich flows a first liquid and, in the inner tube inserted state, forthe double tube to be formed of, at least near a tip of the inner tube,the inner side of the inner tube and the space defined by an outer wallof the inner tube and an inner wall of the insertion hole. With such anarrangement, the double tube has a simple construction, as a result ofwhich production of the joint member is easy.

This insertion hole can be formed by machining or by using a mold havinga mold half that corresponds to the insertion hole. At this time, solong as liquid tightness can be maintained, the inner tube may befastened to the joint member main body while inserted in the insertionhole formed in the joint member or may be attached so as to be removablefrom the joint member main body, although it is preferably attached soas to be removable from the joint member main body. Giving the innertube such a removable structure provides the advantages of facilitatingcleaning of the double tube portion following use and also enablingreplacement in the event that the inner tube is damaged, clogged orcontaminated.

The inner tube fastening and attaching means is not particularlylimited, provided that, as mentioned above, liquid tightness can bemaintained. Examples include fastening with an adhesive, fastening bywelding, and a removable attaching means that involves screw fasteningor the like. The use of a removable attaching means that involves screwfastening or the like is preferred.

It is preferable for the joint member to have a feed port forintroducing a second liquid and for this feed port to be connected tothe insertion hole. This arrangement enables the double tube to be builtat the interior of the joint member main body, as a result of which thelength of the double tube can be shortened, facilitating manufacture ofthe joint member. As with the insertion hole, this feed port also can beformed by machining or by a technique that uses a mold.

The position where the feed port is formed in the joint member is notparticularly limited, although the feed port is preferably formed in adirection orthogonal to the insertion hole. Moreover, from thestandpoint of shortening the double tube length, it is preferable toform the feed port at a position which is closer to the far end of theinsertion hole than the center point between the starting end and thefar end thereof and at a position that can connect with the insertionhole.

In addition, the insertion hole is formed so as to have, in the vicinityof a connecting portion with the feed port, a diameter that issubstantially the same as the inner tube outside diameter, and moreoveris formed so as to have, from the place of connection to the tip of theinner tube, a diameter that is larger than the inner tube outsidediameter. By adopting a hole construction having such differingdiameters, substantially no gap forms between the inner tube and theinsertion hole at the place of connection and so leakage to the startingend side of the insertion hole by the second liquid that flows in fromthe feed port can be prevented, enabling the two liquids to be mixedtogether efficiently.

It is preferable for the joint member to have a hole for connecting tothe static mixer member and for the feed port to be connected to theconnecting hole. This arrangement makes it possible to design the jointmember and the static mixer member separately, which facilitatesadjustment of the internal structure of the mixer for mixing twoliquids. As with the feed port, this connecting hole also can be formedby machining or by a technique that uses a mold.

As with the above-described inner tube, this static mixer member, solong as liquid tightness can be maintained, may be fastened to the jointmember main body while inserted into the connecting hole formed in thejoint member or may be attached so as to be removable from the jointmember main body, although it is preferably attached so as to beremovable from the joint member main body. By making it removable,adjustment in the position of the element body at the interior of thestatic mixer member and cleaning of the mixer following use are simple,in addition to which, in the event of contamination or deterioration,replacement of the parts is possible. The static mixer member fasteningand attaching means is exemplified in the same way as the meansdescribed for the inner tube. Here too, the use of a removable attachingmeans that involves screw fastening or the like is preferred.

In addition, it is preferable for the element body to be inserted intothe interior of the tubular body in such manner that one end thereof issubstantially flush with the double tube side endface of the tubularbody. By thus having the tubular body endface and the end of the elementbody substantially coincide, the two liquids that have flowed out of thedouble tube flow into the element body and mix together at substantiallythe same time as they flow out of the double tube. Hence, more efficientmixing and agitation is carried out from the time of reaction onset.

The shape of the tubular body is not particularly limited. However,taking into consideration the flowability, mixing properties and thelike of the two liquids that pass through the interior, a cylindricalshape is preferred.

The structure of the element body is not particularly limited; use maybe made of an element body that is suitably selected from among thoseused as static mixer element bodies. Illustrative examples include anelement body having a shape in which a plurality of right-handed twistblades and left-handed twist blades mutually overlap in the lengthwisedirection (twist axis direction), an element body having a helical shapewith a fixed direction of twist, and an element body in which arestacked a plurality of plates each provided with one, two or more holes.An element body having a shape in which a plurality of right-handedtwist blades and left-handed twist blades mutually overlap in the twistaxis direction is preferred. By using an element body having such ashape, more efficient mixture is possible and clogging of the mixerduring the reaction is less likely to occur.

The element body may be given a removable structure that only insertsinto the interior of the tubular body or may be given a non-removablestructure that, once inserted, fastens to the tubular body, although aremovable structure that only inserts is preferred. By adopting aremovable structure, positioning of the element body at the interior ofthe tubular body and replacement of the element body are easy.

The diameter of the element body is not particularly limited, so long asthe element body can be inserted into the interior of the tubular body.However, it is preferable for this diameter (maximum diameter) to besubstantially the same as the inside diameter of the tubular body. Inthis way, even in cases where the element body is only inserted into theinterior of the tubular body, the position of the element body can beprevented from varying in both the lengthwise and crosswise directionsat the interior of the tubular body. Taking into account the intendeduse of the mixer for mixing two liquids, the diameter of the elementbody is preferably from about 1 mm to about 10 mm, more preferably fromabout 1.6 mm to about 8 mm, and even more preferably from about 2 mm toabout 5 mm.

The length of the element body is not particularly limited, so long asit can be inserted into the interior of the tubular body, although theelement body length is preferably set to about the same length as thatof the tubular body. This facilitates alignment of the end of theelement with the double tube side endface of the tubular body.

The flow reactor used in this invention is equipped with theabove-described mixer for mixing two liquids. The flow reactor may beequipped with one such mixer or with two or more. In cases where it isequipped with two or more such mixers, multistage flow synthesis ispossible. Because the mixer for mixing two liquids does not readilyclog, pressure loss when flow synthesis is carried out using the flowreactor is low and stable, continuous operation over an extended periodof time is possible, making this flow reactor suitable for large-volumesynthesis.

In addition to the above-described mixer for mixing two liquids, theflow reactor used in this invention may be optionally equipped withvarious other members needed for the reaction, such as a fluid deliverypump, a flow channel-forming tube, and a temperature regulator forregulating the temperature.

The fluid delivery pump is not particularly limited. Use can be made ofa commonly used pump such as a plunger pump, a syringe pump or a rotarypump.

The flow channel-forming tube material is not particularly limited, andmay be a metal such as stainless steel, titanium, iron, copper, nickelor aluminum, or a resin such as polytetrafluoroethylene (PTFE),tetrafluoroethylene-hexafluoropropylene copolymer (FEP), perfluoroalkoxyresin (PFA), polyetheretherketone (PEEK) or polypropylene (PP).

The inside diameter of the flow channel-forming tube may be suitably setaccording to the intended object, within a range that does not detractfrom the advantageous effects of the invention, although in general theinside diameter is preferably from about 0.5 mm to about 10 mm, morepreferably from about 0.7 mm to about 4 mm, and even more preferablyfrom about 1 mm to about 2 mm. The length of the flow channel-formingtube may also be suitably set according to the intended object, within arange that does not detract from the advantageous effects of theinvention, although in general the length is preferably from about 0.1 mto about 20 m, more preferably from about 0.2 m to about 10 m, and evenmore preferably from about 0.3 m to about 5 m.

The mixer for mixing two liquids and the flow reactor used in thisinvention are described more concretely below in conjunction with thediagrams. Referring to FIG. 1, a mixer 1 for mixing two liquids iscomposed of a joint member 2 and a static mixer member 3. The jointmember 2 has a stainless steel main body 21 and a stainless steel innertube 22 (outside diameter, 1.6 mm; inside diameter, 1.0 mm) throughwhich a first liquid flows.

As shown in FIGS. 2 and 3, the main body 21 has an insertion hole 211for inserting an inner tube 22, a feed port 212 for introducing a secondliquid which is orthogonal thereto and connects to the insertion hole211 at the interior of the main body 21, and a static mixermember-connecting hole 213. Female threaded portions 211 a, 212 a and213 a corresponding to male threaded portions formed in the respectivesubsequently described connectors are formed on the inside walls of theinsertion hole 211, the feed port 212 and the connecting hole 213 so asto enable the inner tube 22, a feed tube through which flows a secondliquid, and the static mixer member 3 to be attached to the main body 21by screw fastening.

The insertion hole 211 is composed of, from a starting end side to a farend side thereof: a female threaded portion 211 a, a liquid-tightportion 211 b that is formed continuous therewith and has a trapezoidalcross-sectional shape of reducing diameter which corresponds to theshape at the tip of the subsequently described connector, and an innertube passage 211 c that is formed continuous therewith. Here, referringto FIG. 5, the inner tube passage 211 c of the insertion hole 211 has aninside diameter b that is shaped so as to be substantially the same asthe outside diameter a of the inner tube 22 in the vicinity of aconnecting portion 214 with the feed port 212, and the inner tubepassage 211 c from the connecting portion 214 to the connecting hole 213has an inside diameter c that is shaped so as to be larger than theoutside diameter a of the inner tube 22. In this way, there is provideda structure where, at the connecting portion 214, substantially no gapforms between the inner tube 22 and the insertion hole 211, thuspreventing leakage to the starting end side of the insertion hole 211 bythe second liquid that flows in from the feed port 212. Together withthis, referring to FIG. 6, a double tube 25 is formed by an inner side221 of the inner tube 22 and a space 24 defined by an outer wall 222 ofthe inner tube 22 and an inner wall 211 d of the insertion hole 211.

Also, as shown in FIG. 3, the insertion hole 211 is connected at thestarting end thereof to connecting hole 213. A hole formed of theinsertion hole 211 and the connecting hole 213 thus passes entirelythrough the main body 21.

Referring to FIG. 2, the inner tube 22 has attached thereto a connector23 having a substantially hexagonal columnar head 232 at the interior ofwhich is formed a hole (not shown) through which passes the inner tube22 and which is for screwing, and also, formed integrally therewith, amale threaded portion 231 and a seal 233 in the shape of an invertedtruncated cone for maintaining liquid tightness at the interior of thejoint main body 21. The inner tube 22 is inserted in this state into theinsertion hole 211 having the female threaded portion 211 a, and isattached to the main body 21 by screw fastening.

As shown in FIG. 3, the feed port 212 is composed of, from a startingend side to a far end side thereof, a female threaded portion 212 a, across-sectionally rectangular liquid-tight portion 212 b correspondingto the tip shape of the subsequently described connector, and a couplingportion 212 c that extends from there to the connecting portion 214 withthe insertion hole 211. The insertion hole 211 and the feed port 212 areconnected on the far end side from the midpoint between the starting endand the far end of the insertion hole 211.

As shown in FIG. 3, the static mixer connecting hole 213 is composed of,from a starting end to a far end thereof, a female threaded portion 213a and a cross-sectionally rectangular liquid-tight portion 213 bcorresponding to the tip shape of the subsequently described connector.

Referring to FIGS. 1 and 2, the static mixer member 3 is equipped with acylindrical tubular body 31 (inside diameter, 3.0 mm) made offluoroplastic or stainless steel, and an element body 32 (3 mm diameter)made of polyacetal that is inserted at the interior thereof.

As shown in FIGS. 2 and 4, the element body 32 is inserted into theinterior of the tubular body 31 in a state such that the starting endthereof becomes flush with the endface of the tubular body 31 on thedouble tube 25 side thereof. Here, as shown in FIG. 7, the element body32 has a shape in which a plurality of right-handed twist blades 321 andleft-handed twist blades 322 mutually overlap in a twist axis (centeraxis in longitudinal direction) 323 direction.

Referring to FIG. 2, the top end in the diagram of the cylindrical body31 has formed at the interior a hole (not shown) that passes through thetubular body 31. A fluoroplastic connector 33 having a male threadedportion 331 is attached thereto and, in this state, is inserted into theconnecting hole 213 having female threaded portion 213 a and secured tothe main body 21 by screw fastening.

Next, the internal structure of the mixer for mixing two liquids havingthe above configuration is described while referring to FIGS. 4 to 6. Asmentioned above, the diameter of the insertion hole 211, specificallythe inside diameter b of the inner tube passage 211 c in the vicinity ofthe connecting portion 214 with the feed port 212, is made substantiallythe same as the outside diameter a of the inner tube 22. Also, theinside diameter c of the inner tube passage 211 c from the connectingportion 214 between the insertion hole 211 and the feed port 212 to thetip 223 of the inner tube 22 on the static mixer member 3 side thereofis formed so as to be larger than the outside diameter a of the innertube 22. A double tube 25 is thus formed by the inner side 221 of theinner tube 22 and the space defined by the outside wall 222 of the innertube and the inside wall 211 d of the insertion hole 211.

Also, the double tube 25 side endface of the tubular body 31 in thestatic mixer member 3 and the static mixer member 3 side endface of thedouble tube 25 are in touching contact. In this embodiment, as mentionedabove, because the starting end of the element body 32 is flush with thedouble tube 25 side endface of the tubular body 31, the static mixermember 3 side endface of the double tube 25 and the starting end (topend in FIG. 4) of the element body 32 are also in touching contact.

The second liquid is introduced from the feed port 212. In this case, asshown in FIG. 8, a feed tube 26 through which flows the second liquid isattached and connected by screw fastening to the feed port 212 using aconnector 27 having formed therein a hole (not shown) through whichpasses the feed tube 26 and also having a sealing portion (not shown)for maintaining liquid tightness at the interior of the joint main body21 and a male threaded portion 271.

Next, an embodiment of a flow reactor which uses mixers for mixing twoliquids configured as indicated above is described in conjunction withFIG. 9.

A flow reactor 4 has a construction in which a first mixer 1 a formixing two liquids and a second mixer 1 b for mixing two liquidsdisposed at the interior of a thermostatic chamber 43 are connected inseries via a PTFE tubing 42 d (inside diameter, 1.5 mm).

A pump 41 a for feeding a first liquid is connected to the inner tube 22a of the first mixer 1 a via a PTFE tubing 42 a (inside diameter, 1.0mm). A pump 41 b for feeding a second liquid is connected to a feed portprovided in a main body 21 a of a joint member in the first mixer 1 avia a PTFE tubing 42 b (inside diameter, 1.0 mm) through which flows thesecond liquid and which is provided at the tip thereof with a connector.

A pump 41 c for feeding a third liquid is connected to a feed port inthe second mixer 1 b via a PTFE tubing 42 c (inside diameter, 1.0 mm)through which flows the third liquid and which has a connector providedat the tip thereof, and a PTFE tubing 42 e (inside diameter, 1.5 mm) isconnected to the far end of the static mixer member 3 b of the secondmixer 1 b.

In the flow reactor 4 having such a construction, the respective liquidsfed from the first liquid-feeding pump 41 a and the secondliquid-feeding pump 41 b flow into the joint member main body 21 a ofthe first mixer 1 a for mixing two liquids and pass through the doubletube constructed at the interior thereof, following which they flow intothe static mixer member 3 a that is in touching contact with an end ofthis double tube and, as the liquids are being mixed and agitated by theelement body at the interior thereof, a first reaction arises. A firstreaction mixture following the reaction passes through tubing 42 d,following which it passes through an inner tube 22 b in the second mixer1 b for mixing two liquids and flows into a joint member main body 21 b.This first reaction mixture, together with a third liquid that is fedfrom a third liquid-feeding pump 41 c and flows into the interior of thejoint member main body 21 b, passes through a double tube at theinterior of the joint member main body 21 b and, as in the case of thefirst mixer 1 a for mixing two liquids, flows into the interior of thestatic mixer member 3 b, where a second reaction proceeds.

The mixers for mixing two liquids and the flow reactor that are used inthis invention are not limited to the above-described embodiments.Modifications and improvements may be carried out within a range wherethe objects and advantageous effects of the invention can be achieved.

That is, in the above-described mixer 1 for mixing two liquids, theinner tube 22 and the static mixer member 3 were removably screwfastened to the joint member main body 21. However, these may beremovably arranged by another attaching means or, alternatively, may beconnected and fastened in a non-removable state.

Also, discrete connectors 23 and 33 were provided for the inner tube 22and the tubular body 31. However, instead of providing such discreteconnectors, suitable attaching means may be formed in the inner tube andthe tubular body themselves.

In addition, a feed port 212 was formed in the joint member main body 21in an embodiment that connects with the insertion hole 211 at a rightangle, although an embodiment in which it connects to the insertion holeat another angle is also acceptable. The feed port 212 position also canbe set anywhere.

The material making up the main body 21, inner tube 22 and connector 23was stainless steel but is not limited to this, and may instead beanother metal such as titanium, iron, copper, nickel or aluminum, or maybe a resin such as PTFE, FEP, PFA, PEEK or PP.

The inside diameter of the inner tube 22 may be suitably set accordingto the intended purpose within a range that does not detract from theadvantageous effects of the invention, although normally the insidediameter is preferably from about 0.1 mm to about 3 mm, more preferablyfrom about 0.5 mm to about 2 mm, and even more preferably from about 0.5mm to about 1 mm. The outside diameter of the inner tube 22 may besuitably set according to the intended purpose within a range that doesnot detract from the advantageous effects of the invention, althoughnormally the outside diameter is preferably from about 0.8 mm to about 4mm, more preferably from about 0.8 mm to about 3 mm, and even morepreferably from about 0.8 mm to about 1.6 mm.

The diameter c of the insertion hole 211 may be suitably set accordingto the intended purpose within a range that does not detract from theadvantageous effects of the invention, although normally the insidediameter is preferably from about 0.1 mm to about 5 mm, more preferablyfrom about 0.5 mm to about 4 mm, and even more preferably from about 0.8mm to about 2 mm.

The material making up the tubular body 31 is not limited to stainlesssteel, and may be another metal such as titanium, iron, copper, nickelor aluminum, or a resin such as PTFE, FEP, PFA, PEEK or PP.

The material making up the element body 32 is not limited to polyacetal,and may be another resin such as PTFE, FEP, PFA, PEEK or PP, a metalsuch as stainless steel, titanium, iron, copper, nickel or aluminum, ora ceramic.

The shape of the element body 32 may alternatively be a helical shapewith a fixed direction of twist, or the element body 32 may be one inwhich are stacked a plurality of plates each provided with one, two ormore holes.

The material making up the connector 33 is not limited to afluoroplastic, and may be another resin such as PEEK or PP, or a metalsuch as stainless steel, titanium, iron, copper, nickel or aluminum.

The inside diameter of the tubular body 31 may be suitably set accordingto the intended purpose within a range that does not detract from theadvantageous effects of the invention, although normally the insidediameter is preferably from about 1 mm to about 10 mm, more preferablyfrom about 1.6 mm to about 8 mm, and even more preferably from about 2mm to about 5 mm. The diameter of the element body 32 also may besuitably set according to the intended purpose within a range that doesnot detract from the advantageous effects of the invention, althoughnormally this diameter is preferably from about 1 mm to about 10 mm,more preferably from about 1.6 mm to about 8 mm, and even morepreferably from about 2 mm to about 5 mm.

Because the flow reactor 4 is equipped with two mixers for mixing twoliquids, two-stage flow synthesis is possible. However, in cases wheresingle-stage flow synthesis is carried out, a single mixer for mixingtwo liquids may be used. In cases where n-stage flow synthesis iscarried out, the flow reactor should be assembled in the above-describedmanner using n number of mixers for mixing two liquids.

The inside diameters of tubings 42 a to 42 e in the flow reactor 4 maybe suitably set according to the intended purpose within a range thatdoes not detract from the advantageous effects of the invention,although normally the inside diameter is preferably from about 0.5 mm toabout 10 mm, more preferably from about 0.7 mm to about 4 mm, and evenmore preferably from about 1 mm to about 2 mm. The length also may besuitably set according to the intended purpose within a range that doesnot detract from the advantageous effects of the invention, althoughnormally the length is preferably from about 0.1 m to about 20 m, morepreferably from about 0.2 m to about 10 m, and even more preferably fromabout 0.3 m to about 5 m.

[Polymer Production Method]

The monomer is introduced into the flow reactor in the state of aliquid. At this time, it is preferable for the monomer to be introducedfrom the feed port in the mixer for mixing two liquids. By being thusintroduced, clogging of the flow reactor does not readily arise,pressure loss is suppressed and the polymer can be stably produced overa long period of time.

The solvent that dissolves the monomer is not particularly limited.Preferred examples include ethers such as tetrahydrofuran (THF),2-methyl THF, diethyl ether, tetrahydropyran (THP), oxepane and1,4-dioxane; and also toluene, dichloromethane and diethoxyethane.

The monomer concentration is not particularly limited and may besuitably set according to the intended purpose, although theconcentration is preferably from 0.1 to 5 mol/L, more preferably from0.1 to 3 mol/L, and even more preferably from 0.5 to 2 mol/L. So long asthe monomer concentration is in this range, clogging of the flow reactordoes not readily arise, pressure loss is suppressed, and the polymer canbe stably produced over a long period of time.

The flow rate of the monomer that flows through the flow channel in theflow reactor is not particularly limited and may be suitably setaccording to the intended purpose. The flow rate is preferably from 1 to30 mL/min, more preferably from 5 to 20 mL/min, and even more preferablyfrom 10 to 20 mL/min. So long as the monomer flow rate is in this range,clogging of the flow reactor does not readily arise, pressure loss issuppressed and the polymer can be stably produced over a long period oftime.

The initiator is introduced into the flow reactor in a liquid state. Atthis time, the initiator is preferably introduced from the inner tube ofthe mixer for mixing two liquids. By being thus introduced, clogging ofthe flow reactor does not readily arise, pressure loss is suppressed andthe polymer can be stably produced over a long period of time.

In the polymer production method of the invention, it is especiallypreferable to use n-butyllithium as the initiator. When anionicpolymerization is carried out in a polar solvent (e.g., THF), the rateof polymerization is rapid and so the reaction is generally carried outat a low temperature. Hence, a drawback is that, unless sec-butyllithiumis used as the initiator, the initiation reaction may not proceed asdesired. On the other hand, when anionic polymerization is carried outin a nonpolar solvent (e.g., toluene), the reaction rate is slow andheating is required. In this case, n-butyllithium, which has a lowreactivity, is sometimes used as the initiator. The inventive polymerproduction method using a flow reactor, because reaction at close toroom temperature is possible within a polar solvent, has the advantageof enabling the use of low-reactivity n-butyllithium as the initiator.

The solvent that dissolves the initiator is not particularly limited.Preferred examples include ethers such as hexane, tetrahydrofuran (THF),2-methyl THF, diethyl ether, tetrahydropyran (THP), oxepane and1,4-dixoane; and also toluene, dichloromethane, diethoxyethane, tolueneand diethyl ether.

The initiator concentration is not particularly limited, and may besuitably set according to the type of monomer. The concentration ispreferably from 0.01 to 0.5 mol/L, more preferably from 0.03 to 0.3mol/L, and even more preferably from 0.05 to 0.1 mol/L. At an initiatorconcentration in this range, clogging of the flow reactor does notreadily arise, pressure loss is suppressed and the polymer can be stablyproduced over a long period of time.

The flow rate of the initiator flowing through the flow reactor flowchannel is not particularly limited, and may be suitably set accordingto the intended object. The flow rate is preferably from 0.1 to 10mL/min, more preferably from 0.5 to 5 mL/min, and even more preferablyfrom 1 to 3 mL/min. At an initiator flow rate in this range, clogging ofthe flow reactor does not readily arise, pressure loss is suppressed andthe polymer can be stably produced over a long period of time.

When a flow reactor having two mixers for mixing two liquids, such asabove-described flow reactor 4, is used, a block copolymer can besynthesized. In this case, it is preferable to introduce a secondmonomer from the feed port of the second mixer. Similarly, when a flowreactor having n number of mixers for mixing two liquids is used, ablock copolymer having a maximum of n number of monomer units can besynthesized. The monomer type and concentration, and the flow rate ofmonomer passing through the flow channel in the flow reactor, are thesame as described above.

The reaction temperature (flow reactor temperature) in the productionmethod of the invention is not particularly limited and may be suitablyset according to the desired object. From the standpoint of the reactionrate, the temperature is preferably −80° C. or higher, more preferably−40° C. or higher, and even more preferably −20° C. or higher. From thestandpoint of suppressing side reactions and suppressing deactivation ofthe growing end of the polymer, the reaction temperature is preferablynot more than 100° C., more preferably not more than 50° C., and evenmore preferably not more than 30° C.

Examples of methods for terminating the reaction include the method ofcollecting, in a vessel containing an excess amount of a reactionterminator such as methanol, the polymerization reaction solution thathas exited the flow reactor; and the method of including two or more ofthe above mixers for mixing two liquids in the flow reactor and having areaction terminator such as methanol flow from one side of the finalmixer for mixing two liquids.

With the production method of the invention, a polymer having a smalldispersity Mw/Mn (a narrow molecular weight distribution) can besynthesized. The dispersity is preferably not more than 1.5, morepreferably not more than 1.3, even more preferably not more than 1.2,and still more preferably not more than 1.15. Mw and Mn respectivelyrepresent the weight-average molecular weight and number-averagemolecular weight, these being polystyrene equivalent measured valuesobtained by gel permeation chromatography (GPC). The Mw of the polymerobtained by the production method of the invention, although notparticularly limited, is preferably from 1,000 to 100,000, and morepreferably from 1,000 to 50,000.

[Polymer]

The polymer obtained by the polymer production method of the inventionincludes structural units of formula (1) below

(in the formula, R¹ to R⁶ are the same as above) and has an end that isan n-butyl group from an initiator residue, a weight-average molecularweight (Mw) of from 1,000 to 50,000, and a dispersity of 1.5 or less.

Such a polymer can be produced by, in the above-described polymerproduction method, using the above-described styrene derivative as themonomer and using n-butyllithium as the initiator.

The polymer production method of the invention is particularly suitablefor producing a block copolymer that includes a first polymer blockcontaining structural units of formula (2) below and a second polymerblock containing structural units of formula (3) below

wherein the structural units of formula (2) and the structural units offormula (3) are mutually differing structural units and the polymer hasan end that is an n-butyl group from an initiator residue, aweight-average molecular weight (Mw) of from 1,000 to 50,000, and adispersity of 1.5 or less.

In the above formulas, R¹¹ and R²¹ are each independently a hydrogenatom or a methyl group; 10² to 10⁶ are each independently a hydrogenatom, an alkoxy group of 1 to 5 carbon atoms or an alkyl group of 1 to10 carbon atoms which may be substituted with a halogen atom; R²² to R²⁶are each independently —OSiR²⁷ ₃ or —SiR²⁷ ₃; each R²⁷ is independentlyan alkyl group of 1 to 10 carbon atoms, a phenyl group, an alkoxy groupof 1 to 5 carbon atoms or an alkylsilyl group of 1 to 5 carbon atoms;and m and n represent the number of respective structural units, eachbeing independently an integer from 1 to 480. The alkyl group, alkoxygroup and halogen atom are exemplified in the same way as describedabove.

R¹⁴ is preferably an alkoxy group of 1 to 5 carbon atoms, and morepreferably a methoxy group. R²⁴ is preferably −SiR²⁷ ₃, and morepreferably —Si(CH₃)₃. R¹², R¹³, R¹⁵, R¹⁶, R²², R²³, R²⁵ and R²⁶ are eachpreferably a hydrogen atom, an alkyl group of 1 to 10 carbon atoms, analkoxy group of 1 to 5 carbon atoms or —SiR⁷ ₃; and more preferably ahydrogen atom, a methoxy group or —Si(CH₃)₃.

In the above-described block copolymer, the first polymer block ispreferably one containing only structural units of formula (2), and thesecond polymer block is preferably one containing only structural unitsof formula (3). The block copolymer is preferably one containing onlythe first polymer blocks and the second polymer blocks.

In the above-described block copolymer, the content ratio of the firstpolymer blocks and the second polymer blocks, expressed in terms of themolar ratio, is preferably from 1:1 to 1:10, and more preferably from1:1 to 1:3.

This block copolymer can be produced by using, as the monomers in theabove-described polymer production method, a monomer that givesstructural units of formula (1) and a monomer that gives structuralunits of formula (2), using n-butyllithium as the initiator, and using aflow reactor having two or more mixers for mixing two liquids.

EXAMPLES

Synthesis Examples, Working Examples and Comparative Examples are givenbelow to more concretely illustrate the invention, although theinvention is not limited by these Examples.

FIG. 10 shows a schematic view of the flow reactor used in the WorkingExamples and Comparative Examples described below. In FIG. 10, thearrows indicate the direction of liquid flow. A plunger pump (KP-12 orHP-12, from Flom K. K.) was used for feeding liquid A, and PTFE tubing(inside diameter, 1.0 mm; outside diameter, 1.6 mm; length, 2 m) wasused to connect the plunger pump and Mixer 1. A syringe pump 1(Keychem-L, from YMC Co., Ltd.; Working Examples 1 to 7) or a diaphragmpump 1 (Smoothflow-Q, from Tacmina Corporation; Working Examples 8 to10) was used for feeding liquid B, and PTFE tubing (inside diameter, 1.0mm; outside diameter, 1.6 mm; length, 2 m) was used to connect thesyringe pump 1 and Mixer 1. The Mixer 1 outlet and an inlet to Mixer 2were connected by PTFE tubing 1 (inside diameter, 1.5 mm; outsidediameter, 3 mm; length: 2 m (Working Examples 1-4 and 7), 5 m (WorkingExamples 5 and 6), 1.3 m (Comparative Example 1) or 0.7 m (ComparativeExample 2)) or PFA tubing 1 (inside diameter, 2 mm; outside diameter, 3mm; length, 1 m (Working Examples 8 to 10)). The other Mixer 2 inlet wasconnected to a syringe pump (Asia, from Syrris Ltd.) for feeding liquidC by PTFE tubing (inside diameter, 1.0 mm; outside diameter, 1.6 mm;length, 2 m). PTFE tubing 2 (inside diameter, 1.5 mm; outside diameter,3 mm; length: 2 m (Working Examples 1 to 7), 1.3 m (ComparativeExample 1) or 0.7 m (Comparative Example 2)) or PFA tubing 2 (insidediameter, 2 mm; outside diameter, 3 mm; length, 0.7 m (Working Examples8 to 10)) was connected to the Mixer 2 outlet. Liquids A, B and C weremade to flow into the reactor at respective flow rates X, Y and Z(mL/min), thereby effecting the reaction, and the effluent was analyzedby gel permeation chromatography (GPC). The flow channels downstream ofthe respective pumps and up to nine-tenths of the length of the tubing 2were immersed in a thermostatic chamber at T° C. and the temperature wasregulated. The pressure sensor log for the fluid A pump was set toindicate the pressure trend.

The GPC measurement conditions were as follows.

-   -   Column: PLgel 3 μm MIXED-E (Agilent Technologies)    -   Mobile phase: tetrahydrofuran (THF)    -   Flow rate: 1.0 mL/min    -   Column oven: 40° C.    -   Detector: UV detector    -   Dose: polystyrene standard

The ¹H-NMR (300 MHz) measurement conditions were as follows.

-   -   Measurement solvent: heavy chloroform    -   Reference substance: tetramethylsilane (TMS) (δ0.0 ppm)

Table 1 shows collectively, for Working Examples 1 to 10 and ComparativeExamples 1 and 2, the compositions of liquids A to C and their flowrates X to Z (mL/min), as well as the temperature T (° C.) of thethermostatic chamber.

TABLE 1 X Y Z T Liquid A (mL/min) Liquid B (mL/min) Liquid C (mL/min) (°C.) Working 1 2.0 mol/L 10 0.11 mol/L 2 0.25 mol/L 10 5 Examplestyrene/THF sec-butyllithium/hexane MeOH/THF 2 0.5 mol/L 10 0.06 mol/L 20.25 mol/L 10 5 4-methoxystyrene/THF sec-butyllithium/hexane MeOH/THF 30.5 mol/L 10  0.1 mol/L 2 0.25 mol/L 10 5 4-methoxystyrene/THFn-butyllithium/hexane MeOH/THF 4 0.65 mol/L  5 0.05 mol/L 2 0.25 mol/L5.5 5 4-trimethylsilylstyrene/THF n-butyllithium/hexane MeOH/THF 5 0.5mol/L 10 0.05 mol/L 2 0.65 mol/L 5 5 4-methoxystyrene/THFn-butyllithium/hexane 4-trimethylsilylstyrene/THF 6 0.5 mol/L 10 0.05mol/L 2 0.25 mol/L 5.5 5 4-methoxystyrene/THF n-butyllithium/hexaneMeOH/THF 7 2.0 mol/L 10 0.11 mol/L 2 0.25 mol/L 10 −20 styrene/THFn-butyllithium/hexane MeOH/THF 8 1.0 mol/L 30 0.10 mol/L 6 0.50 mol/L 100 styrene/THF n-butyllithium/hexane MeOH/THF 9 1.0 mol/L 40 0.10 mol/L 80.50 mol/L 10 0 styrene/THF n-butyllithium/hexane MeOH/THF 10 0.65mol/L  30 0.10 mol/L 6 0.50 mol/L 10 0 4-trimethylsilylstyrene/THFn-butyllithium/hexane MeOH/THF Comparative 1 1.0 mol/L 5 0.11 mol/L 10.25 mol/L 6.3 5 Example 4-methoxystyrene/THF sec-butyllithium/hexaneMeOH/THF 2 2.0 mol/L 5  0.1 mol/L 1 0.25 mol/L 6.1 −20 styrene/THFsec-butyllithium/hexane MeOH/THF

Working Example 1

The reaction was carried out under the conditions in Table 1. The jointmember 2 used in Mixer 1 was made of stainless steel and the tubularbody 31 was made of fluoroplastic. The static mixer element bodyconsisted of DSP-MX3-17 polyacetal elements from Noritake Company Ltd.(17 twist blades; diameter 3 mm) that were modified by joining threesuch elements together to bring the number of twist blades to 51. Mixer2 was made of the same materials as Mixer 1, and modified DSP-MXA3-17elements were used as the static mixer element body here too. The liquidA tubing was connected to the feed port inlet on Mixer 1, and the liquidB tubing was connected to the inner tube inlet. The liquid C tubing wasconnected to the feed port inlet on Mixer 2, and Tubing 1 was connectedto the inner tube inlet. Unless noted otherwise, the same manner ofconnection was used below in the other Examples. After 10 minutes ofliquid feeding, the effluent was collected for one minute. This effluentwas analyzed by GPC, whereupon Mn=14,313 and Mw/Mn=1.15.

FIG. 11 shows the pressure trend during the reaction. There weresubstantially no pressure fluctuations over 10 minutes.

Working Example 2

The reaction was carried out under the conditions in Table 1. The samematerials as in Working Example 1 were used for Mixer 1. In the staticmixer member, an element body having 68 twist blades obtained bymodifying and joining together four DSP-MXA3-17 elements and an elementbody having 51 twist blades obtained by modifying and joining togetherthree DSP-MXA3-17 elements were connected in series and used. Mixer 2was the same as that used in Working Example 1. After 20 minutes ofliquid feeding, the effluent was collected for one minute. This effluentwas analyzed by GPC, whereupon Mn=6,327 and Mw/Mn=1.08.

FIG. 12 shows the pressure trend during the reaction. There weresubstantially no pressure fluctuations over 20 minutes.

Working Example 3

The reaction was carried out under the conditions in Table 1. The samematerials as in Working Example 2 were used for Mixers 1 and 2. After 15minutes of liquid feeding, the effluent was collected for one minute.This effluent was analyzed by GPC, whereupon Mn=4,026 and Mw/Mn=1.07.

FIG. 13 shows the pressure trend during the reaction. There weresubstantially no pressure fluctuations over 15 minutes.

Working Example 4

The reaction was carried out under the conditions in Table 1. The samematerials as in Working Example 1 were used for Mixer 1. In the staticmixer member, an element body having 68 twist blades obtained bymodifying and joining together four DSP-MXA3-17 elements was used. Mixer2 was the same as that used in Working Example 2. After 10 minutes ofliquid feeding, the effluent was collected for one minute. This effluentwas analyzed by GPC, whereupon Mn=9,857 and Mw/Mn=1.34.

FIG. 14 shows the pressure trend during the reaction. There weresubstantially no pressure fluctuations over 10 minutes.

Working Example 5

The reaction was carried out under the conditions in Table 1. The samematerials as in Working Example 2 were used for Mixers 1 and 2. After 20minutes of liquid feeding, the effluent was collected for one minutewhile adding dropwise 10 mL of a 0.25 mol/L methanol/THF solution. Thiseffluent was analyzed by GPC, whereupon Mn=20,343 and Mw/Mn=1.15.

FIG. 15 shows the pressure trend during the reaction. There weresubstantially no pressure fluctuations over 20 minutes.

In addition, the solvent was driven off with an evaporator from 308 g ofthe effluent, bringing the volume down to 125 g, after which 501 g ofmethanol was added dropwise at room temperature. The resulting whitesuspension was filtered with filter paper (No. 5B from Kiriyama GlassCo.) and then washed with 153 g of methanol. Next, the resulting whitesolid was vacuum dried (50° C., 2.5 hours), giving 16 g ofpolymethoxystyrene-b-polytrimethylsilylstyrene block copolymer. FIG. 16shows the ¹H-NMR chart of the resulting polymer.

Working Example 6

The reaction was carried out under the conditions in Table 1. Aside fromthe tubular body 31 of Mixer 1 being made of stainless steel, the othermembers thereof and Mixer 2 were the same as those used in WorkingExample 2. After 20 minutes of liquid feeding, the effluent wascollected for one minute. This effluent was analyzed by GPC, whereuponMn=10,700 and Mw/Mn=1.10.

FIG. 17 shows the pressure trend during the reaction. There weresubstantially no pressure fluctuations over 15 minutes.

Working Example 7

The reaction was carried out under the conditions in Table 1. Aside fromthe tubular bodies 31 of Mixers 1 and 2 being made of stainless steel,the other members were the same as those used in Working Example 1.After 15 minutes of liquid feeding, the effluent was collected for oneminute. This effluent was analyzed by GPC, whereupon Mn=11,544 andMw/Mn=1.15. There were substantially no pressure fluctuations over 15minutes.

Working Example 8

The reaction was carried out under the conditions in Table 1. In Mixer1, the same materials were used as in Working Example 1. In Mixer 2, anordinary simple double-tube mixer was used. After 3 minutes of liquidfeeding, the effluent was collected for 0.5 minute. This effluent wasanalyzed by GPC, whereupon Mn=5,979 and Mw/Mn=1.08.

Working Example 9

The reaction was carried out under the conditions in Table 1. In Mixer1, the same materials were used as in Working Example 1. In Mixer 2, anordinary simple double-tube mixer was used. After 3.5 minutes of liquidfeeding, the effluent was collected for 0.5 minute. This effluent wasanalyzed by GPC, whereupon Mn=5,956 and Mw/Mn=1.09.

Working Example 10

The reaction was carried out under the conditions in Table 1. In Mixer1, the same materials were used as in Working Example 1. In Mixer 2, thesame materials were used as in Working Example 8. After 3.5 minutes ofliquid feeding, the effluent was collected for 0.5 minute. This effluentwas analyzed by GPC, whereupon Mn=6,566 and Mw/Mn=1.09.

Comparative Example 1

The reaction was carried out under the conditions in Table 1. A T-mixer(from Sanko Seiki Kogyo K K; made of stainless steel; inside diameter,0.25 mm) was used as Mixer 1. The respective pumps were connected sothat liquid A and liquid B meet at 180°. A T-mixer (from Sanko SeikiKogyo K K; made of stainless steel; inside diameter, 1.0 mm) was used asMixer 2. The respective pumps were connected so that the liquid thatemerges from Mixer 1 and liquid C meet at 180°.

FIG. 18 shows the pressure trend during the reaction. Sudden pressurefluctuations are apparent starting about 5 minutes after liquid feeding.

Comparative Example 2

The reaction was carried out under the conditions in Table 1. Comet X-01mixers (stainless steel mixers from Techno-Applications KK) were used asMixers 1 and 2. In Mixer 1, the liquid A tubing was connected to theinlet side of the outer tube, and the liquid B tubing was connected tothe inner tube inlet. In Mixer 2, the liquid C tubing was connected tothe inlet side of the outer tube, and Tubing 1 was connected to theinner tube inlet.

FIG. 19 shows the pressure trend after 35 minutes of liquid feeding.Some pressure fluctuation and a rise in pressure over time are apparent.

As demonstrated above, with the polymer production method of theinvention, clogging of the flow channels in the flow reactor did notreadily occur, as a result of which pressure fluctuations were notobserved and the polymer was stably produced over a long period of time.

REFERENCE SIGNS LIST

1 Mixer for mixing two liquids

2 Joint member

21 Main body

211 Insertion hole

212 Feed port

213 Connecting hole

22 Inner tube

221 Inner side of inner tube

222 Outer wall of inner tube

223 Inner tube tip

24 Space

25 Double tube

3 Static mixer member

31 Tubular body

32 Element body

321 Right-handed twist blade

322 Left-handed twist blade

4 Flow reactor

1. A polymer containing structural units of formula (1) below

where R¹ is a hydrogen atom or a methyl group; R² to R⁶ are eachindependently a hydrogen atom, an alkoxy group of 1 to 5 carbon atoms,an alkyl group of 1 to 10 carbon atoms that may be substituted with ahalogen atom, —OSiR⁷ ₃ or —SiR⁷ ₃; and each R⁷ is independently an alkylgroup of 1 to 10 carbon atoms, a phenyl group, an alkoxy group of 1 to 5carbon atoms or an alkylsilyl group of 1 to 5 carbon atoms, wherein thepolymer has an end that is an n-butyl group from an initiator residue, aweight-average molecular weight of from 1,000 to 50,000, and adispersity is 1.5 or less.
 2. The polymer of claim 1, wherein R⁴ is analkoxy group of 1 to 5 carbon atoms or —SiR⁷ ₃.
 3. The polymer of claim1, wherein R⁴ is a methoxy group or —Si(CH₃)₃.
 4. A block copolymercomprising a first polymer block containing structural units of formula(2) below and a second polymer block containing structural units offormula (3) below

where R¹¹ and R²¹ are each independently a hydrogen atom or a methylgroup; R¹² to R¹⁶ are each independently a hydrogen atom, an alkoxygroup of 1 to 5 carbon atoms or an alkyl group of 1 to 10 carbon atomswhich may be substituted with a halogen atom; R²² to R²⁶ are eachindependently a hydrogen atom, —OSiR²⁷ ₃ or —SiR²⁷ ₃; each R²⁷ isindependently an alkyl group of 1 to 10 carbon atoms, a phenyl group, analkoxy group of 1 to 5 carbon atoms or an alkylsilyl group of 1 to 5carbon atoms; and m and n are each independently an integer from 1 to480, wherein the structural units of formula (2) and the structuralunits of formula (3) are mutually differing structural units and thepolymer has an end that is an n-butyl group from an initiator residue, aweight-average molecular weight (Mw) of from 1,000 to 50,000, and adispersity of 1.5 or less.
 5. The block copolymer of claim 4, whereinR¹⁴ is an alkoxy group of 1 to 5 carbon atoms and R²⁴ is —SiR²⁷ ₃. 6.The block copolymer of claim 5, wherein R¹⁴ is a methoxy group and R²⁴is —Si(CH₃)₃.